Process of treating cellulosic textiles with methylol derivatives of tris(2-carbamoylethyl) phosphine and products thereof



United States Patent F PROCESS OF TREATING CELLULOSIC TEXTILES WITHMETHYLOL DERIVATIVES OF TRIS(2- CARBAMOYLETHYDPHOSPHINE AND PROD- UCTSTHEREOF Leon H. Chance, New Orleans, and George L. Drake, Jr., andWilson A. Reeves, Metairie, La., assiguors to the United States ofAmerica as represented by the Secretary of Agriculture No Drawing.Original application Feb. 8, 1963, Ser. No. 257,342. Divided and thisapplication Feb. 24, 1964,

Ser. No. 355,137

4 Claims. (Cl. 8116.3)

This application is a division of Serial No. 257,342, filed February 8,1963.

A nonexclusive irrevocable, royalty-free license in the invention hereindescribed, throughout the world for all purposes of the United StatesGovernment, with the power to grant sublicenses for such purposes, ishereby granted to the Government of the United States of America.

This invention relates to tris(2-carbamoylethyl)phosphine having theformula The reaction may be carried out over :a temperature range offirom about 25 to 100 C. with the formation of the desired product andethanol. The reaction proceeds more rapidly at the higher temperatures,and in some cases at the higher temperatures it is desirable to carryout the reaction at pressures greater than atmospheric pressure.

The reaction is carried out in the presence of aqueous ammonia. In somecases the reaction may be facilitated by adding a water soluble alcoholsuch as ethanol or methanol. The function of thealcohol is to bring theester into solution in the aqueous ammonia. Upon completion of thereaction, the desired product may be separated by evaporation of aportion 'of the solvent and allowing the product to crystallize. Thetris(2-carbamoylethyl)ph osph|ine is a White crystalline solid and isweakly basic in character.

In an alternative process, tris(2acarbamoylethyl)phosphine may beprepared by acid hydrolysis of tris(2-cyanoethyDphosphine having theformula the hydrolysis to produce tris(2-carbamoylethyl)phosphine. Uponcompletion of the reaction the mixture is neutralized with a base suchas ammonia or sodium by- Patented Oct. 4, 1966 droxide, and the productallowed to crystallize from the solution.

T1is(2-carbamoy1ethyl)phosphine reacts readily with formaldehyde inaqueous acid or alkaline solution to form the N-met-hylol derivatives.Alkaline conditions are preferred for preparation of the methylolderivatives. In an acid system the formaldehyde reacts With the amidewithin the range of and including the mole ratios of 1 to l and 1 to 6to fiorm the water soluble methylol derivatives, then these begin tocondense to form insoluble fl'ame resistant polymers. Six moles offormaldehyde per mole of the phosphine can react, but the derivativescontaining one, two, or three methylol groups are the most stable. Bestresults are obtained on a cellulosic textile when three moles ofform-aldehyde react.

Cellulosic textile fiber, yarns and fabrics can be made fl'ameresistant, crease resistant, rot resistant, resistant to damage bychlorine bleaching, and dimensionally stable in accordance with thisinvention. The process consists essentially of impregnating the textilematerials with an aqueous solution of the methylol derivatives andcuring the impregnated materials at the temperatures conventionally usedfor curing cellulosic textiles.

The time and temperature required for the cure is partially dependentupon the weight of fabric being treated.

ening agents improve the hand and tearing strength of cotton and rayontextiles.

Simultaneous polymerization within and crosslinking of the cellulosemolecules of the fibers provided by this invention are produced in thepresence of an 'acidcatalyst. Catalysts suitable for the reaction arethose conventionally employed in applying methylol amides to cellulosicmaterials which are Lewis and protonic acids. They include latent acidcatalysts such as magnesium chloride, zinc nitrate, zinc fluoborate, andamine hydrochlorides.

When a cotton textile is being treated, it is of advantage to pass itthrough the impregnating liquor to thoroughly wet it and remove theexcess liquor by passing the textile through squeeze rolls. It isalso'advantageous to 'dry the textile at a temperature of about 60 to C.before curing. The preferred curing conditions are from about to C. for10 to 1 minute using the longer time for the lower temperature.

The degree of flame resistance and crease resistance can be varied froma low to a high degree by varying the amount of polymer and crosslinkingput into the textile. Considerable improvement in dimensional stabilityis obtained with as little as 1% add-on of the finish. About 3 to 15%add-on is needed for a high degree of improvement in crease resistanceand smooth drying properties of a cotton fabric.

Some advantages of treating cotton textiles in accordance with thisinvention are: flame and glow resistance, shrink resistance, rot andmildew resistance, crease resistance, permanence to laundering and drycleaning, and resistance to damage caused by chlorine bleachingtollowe'd by scorching. The presence of the phosphine group is ofparticular value in this textile finish because of its slight baseproperties. The phosphine group is sufficiently basic to neutralize thedegrading action of acids on cellulous when the textile is exposed tosunlight or to elevated temperatures as by ironing.

The following examples are illustrative of the invention: The textiletesting data shown in the examples were obtained by standard methods ofthe American Association of Textile Chemists and Colorirsts. All partsare by weight.

EXAMPLE 1 T ris(2-carbam0ylethyl phosphine (Method 1Tris(Z-carbethroxyethyl)ph-osphine 17.0 parts) and concentrated aqueousammonia containing 28.7% ammonia (50.0 parts) were stirred together for16 hours at room temperature. A portion of the ester still remainedundissolved. Ethanol (10 parts) was added to bring the ester intosolution. The solution was placed in a closed reaction Vessel and heatedfor three hours at 95 to 100 C. under autonomous pressure. The vesselwas cooled and the resulting solution evaporated until the solutionbecame slightly viscous. The solution was cooled and white crystalsseparated. The crystals were insoluble in benzene, acetone, chloroform,ethyl acetate, and ethyl alcohol, and slightly soluble in cold water.Pure crystals melting at 191.5-192.5 C. (corrected) were obtained onrecrystallizing from hot water. Infnared absorption data showed thepresence of amide groups.

Analyses.--Calculated for C H N O P: C, 43.72; H, 7.34; N, 16.98; P,12.53. Found: C, 43.55; H, 7.36; N, 16.86; P, 12.77.

EXAMPLE 2 Tris(Z-carbamoylethyl)phsphine (Method 2) T ris(2-cyanoethyl)phosphine (9.65 parts) and water (2.7 parts) were placed in a flaskcontaining 1,4-dioxane (60 parts). The flask was equipped with amechanical stirrer, thermometer, gas diffusion tube, and refluxcondenser. The flask was also equipped for external cooling. Whilestirring dry hydrogen chloride (5.5 par-ts) was bubbled into the mixtureWhile maintaining the temperature below 45 C. by external cooling. Aviscous material separated during the reaction. The dioxane was decantedfrom the viscous material. Water (10 parts) was added to the, viscousmaterial to dissolve it. The water solution was neutralized withconcentrated ammonium hydroxide. The solution was cooled in arefrigerator, and white crystals separated. The crystals were identicalwith those obtained by Method 1.

EXAMPLE 3 Methylol derivative of tris(2-carbamoylethyl)phosphineTris(2-oarbamoylethy l)phosphine (2.4 parts) was added to water (10parts). Aqueous formaldehyde 2.7 parts of 36.3% formaldehyde) was addedand the pH adjusted to 11 with dilute sodium hydroxide solution. Thecrystals dissolved, and the solution was allowed to stand at roomtemperature for about 20 hours. The mole ratio of the phosplhine toformaldehyde was 1:3. The resulting solution consisted largely of thetrimethyl ol derivative of tris(2-carbamoylethyl)phosphine.

EXAMPLE 4 The solution obtained from Example 3 was adjusted to a 'pH of4.5 with concentrated hydrochloric 'acid. Magnesiu-m chloridehexahydrate (0.33 part) was added and the solution diluted with water(6.5 parts). The resulting solution contained approximately 15% of thetrirnethylol derivative and 1.5% magnesium chloride hexahydrate. Thefinal pH of the solution was 4.5. The solution was padded on to cottonprint cloth to a wet pickup of -about The fabric was dried in a forceddraftoven at 60 C. for 7 minutes and then cured in the same oven at C.for 3 minutes. The fabric was washed and dried. The fabric had an add-onof 15 It exhibited considerable flame resistance and left a toughcharred material which retained the fabric'structuren There was no.afterglow. The wet wninkle recovery was 267 and the dry wrinkle recoverywas 274 as measured by the Monsanto wrinkle. recovery tester. Thewrinkle recovery of the untreated print cloth was 160 (wet) and 179(dry). Wrinkle recovery values are the sum of warp and fillingdirections. The ifabric retained 91% of its strength after chlorinebleaching followed by scorching. The fabric was shrink resistant andresistant to mildew and rot.

We claim:

1. A process for treating cellulosic textile materials to render themdimensionally stable and flame-, crease-, and rot-resistant whichcomprises wetting the, cellulosic textile material with an aqueoussolution of (a) a water-soluble methylol derivative oftris(2-carbamoylethyl)phosphine obtained by reacting, at roomtemperature and in an acidic aqueous solution, tris(2-carbamoy1ethyl)phosphine with aqueous formaldehyde within the range of and includingthe mole ratios of 1 to 1 and 1 to 6, and

(b) an acid type catalyst and heat curing the so wetted cellulosictextile material to the dried state.

2. The process of claim 1 wherein the water-soluble methylol derivativeof tris(Z-carbamoylethyl)phosphine is obtained by reacting, at roomtemperature and in alkaline aqueous solution,tris(2-carbamoylethyl)phosphine with aqueous formaldehyde in the ratioof, 1 mole of tris(2-carbamoylethyl phosphine to 3 moles offormaldehyde.

3. A dimensionally stable and flame-, crease, and rotresistantcellulosic textile produced by the process of claim 1.

4. A dimensionally stable and flame-, crease-, and rotresistantcellulosic textile material produced by the process of claim 2.

References Cited by the Examiner UNITED STATES PATENTS 1 10/ 1957 Reeveset a1. 8116.3 11/1957 Reeves et a1. 8116.3

1. A PROCESS FOR TREATING CELLULOSIC TEXTILE MATERIALS TO RENDER THEMDIMENSIONALLY STABLE AND FLAME-, CREASE-, AND ROT-RESISTANT WHICHCOMPRISES WETTING THE CELLULOSIC TEXTILE MATERIAL WITH AN AQUEOUSSOLUTION OF (A) A WATER-SOLUBLE METHYLOL DERIVATIVE OFTRIS(2-CARBAMOYLETHYL)PHOSPHINE OBTAINED BY REACTING, AT ROOMTEMPERATURE AND IN AN ACIDIC AQUEUOUS SOLUTION,TRIS(2-CARBAMOYLETHYL)PHOSPHINE WITH AQUEOUS FORMALDEHYDE WITHIN THERANGE OF AND INCLUDING THE MOLE RATIOS OF 1 TO 1 AND 1 TO 6, AND (B) ANACID TYPE CATALYST AND HEAT CURING THE SO WETTED CELLULOSIC TEXTILEMATERIAL TO THE DRIED STATE.